Vat dye composition and manufacture thereof



Patented Jan. 19, 1937 VAT DYE COMPOSITION AND MANU-s FACTURE THEREOF Jean G. Kern, East Aurora, N. Y, assignor to National Aniline & Chemical Company, Inc., New York, N. Y., a corporation of New York UNITED STATES No Drawing. Original application May 26, 1933,

Serial No. 673,031.

Divided and this application February 7, I936, Seral No. 62,867

b 20 Claims. This invention relates to vat dye compositions and processes for their manufacture.

'Fhe' dyeing of textile fibers with'vat dyes in t :volves absorptionor adsorption by the fiber of the dye in a soluble form followed by a fixing treatment, to render insoluble the dye taken up by the fiber, and other finishing operations for removing undesired residual material. It is well I known that vat dyes are solid substances which are insoluble in water. In order to render them useful in the dyeing of textile fibers, they are, ordinarily converted to a water soluble form, as

for example, by treatment with a reducing agent, such as sodium hydrosulfite and alkali. b Two general methods are ordinarilyemployed in practice for dyeing fibers with vatdyes. In accordance with one method, a solution or dye bath containing the vat dye in the reduced form 1 (a so-called vat) is first prepared, the material to be dyed is worked, in this solution or bath whereby the fiber takes up the reduced compound of the dye, and the material is then subjected to oxidation and otherfinishing treatments to coni vert the vat dye from the reduced to the unreduced form and further complete the fixing of the dye and finishing of the material. In accordance with another method, the dye is applied to the mater al to be dyed while in the unreduced formpit is then subjected to a reducingv treatment whereby the dye is converted to the soluble form in the presence of the fiber and is taken up by the fiber, and his then subjected to oxidation and/or other finishing treatments to fix ,the dye on the fiber and complete the finishing of the material.

In dyeing with vat dyes by the latter method, one, of two procedures is usually followed, it depending upon whether the material is to be dyed a uniform or so-called solid color, or is to be dyed in, accordance with a pattern or design in one or more colors. If the material is to be dyed a solid color, the so-called pigment padding or pad and jig process is ordinarily employed. If the material is to be dyed in accordance with a pattern or design, the so-called printing process is generally utilized.

The pigment padding process of dyeing with vat dyes generally involves passing the textile material to be dyed through an aqueous suspension or so-called padding bath containingthe unreduced vat dyein finely divided-form suspended in a suitable suspension medium (such as water, which mayor may not also contain a gum or thickener and other substances such as an assistant, sodium sulfide, etc.), whereby the fiber mechanically picks up the particles of insoluble dye; subsequently working the textile material, having the particles of dye mechanically attached thereto, in-a reducing bath (jigging) whereby the dye isreduced to the soluble form andis taken (absorbed and/or adsorbed) by the fiber; and finally subjecting the material to oxidation and'finishing treatments to reconvert the dye to the insoluble form, fix it on the fiber,

and further complete the finishing ofthe material.

The printing process of dyeing textile fabrics generally involves applying a so-called printing paste to the fabric in the form of a design (for example, by means of a screen, a stencil or an engraved roll), and then subjecting the printed fabric to further treatment to fixthe dye. In general, vat dye printing pastes contain, in addition to the unreduced vat dye, substances which in themselves do not reduce the vat dye under the conditions of the printing operation but which in the subsequent operations react with the dye tojconvert it to the soluble form (such as sodium fcrmaldehydesulfoxylate and potassium carbonate), other substances or assistants which promote the reduction of thedye and/or absorption of the reducedcompound' by the fiber, and

suitable gums or thickeners. In some cases, as in printing with diificultly reducible vat dyes, the vat dye in the printing paste is subjected to a preliminary reductionbefore applying the printing paste to the fabric. The fixing treatment usually comprises subjectingthe printed fabric to a short treatment with wet steam while ex eluding air (so-called steaming or ageing), whereby the vat dye is reduced (for example, by the action of the -sodium-iormaldehyde-sulfoxylate and potassium carbonate), or if prereduced its reduction'is .rendered more com,-

plete, and the reduced .dye is taken up by the fiber; and then subjecting the printed fabric to oxidizing, washing and other finishing treatments.

The vat dyes in the Ordinary unreduced, solid form are not only insoluble in water but they are not readily wetted by water, and even when ground with water for a considerable length of time do not disperse uniformly in the extremely finely divided form desired for use in dyeing by the pigment. padding and printing processes. They therefore usually come upon the market in the form of aqueous suspensions or so-called pastes which generally contain 10 to per cent. of the vat dye, a small amount of adispersing. agent such as Leukanol (a condensation On Y of a precipitate of the dye, as obtained for exam.- ple in its manufacture or by precipitation in the finely divided form from a vat or from a sulfuric acid or other solution.

-- Vat dye pastes as ordinarily prepared,however,

have a number of disadvantages from the standpoint of economy. For example they contain a" preponderating quantity of material which .has

- no dyeing action (mainly water) which addsconsiderably to the cost of transportationand handling of the active dye material; care must be exercised in the transportation of the pastes in order to avoid loss of the material by leakage of the container; precautions must'be taken in' winter to prevent freezing; care must be exercised in the storage of'the paste tojavoid drying? out and formation "of an insoluble crust which does notredisperse and which frequently appears as specksin the paste causing imperfections'in the resulting dyeings and prints; and upon standing the pastes frequently settle andrequire thorough agitation to produce uiform dispersion, which is time-, and labor-consuming- Various attempts heretofore have been made to provide vat dyes in the dry or powder'form which will wet and disperse to a sufficient'extent to be useful for the dyeings of textile fibers by all processes. Thus, vat dye powders have. been produced by drying pastes of vat .dyes. In some cases dispersing agents havev been incorporated into the vat dye pastes prior to the drying. While the'resultingpowders frequently have improved wetting and dispersing qualities I as compared with powders produced by grinding dry vat dye stuffs, when converted into a paste byfs'lurrying with water and/or when incorporated in a printing paste,-they do .not produce" a dispersion of the vat dye which possesses the" suitability for dyeing comparable with that of the ordinary commercial vat dye pastes. The principal'difiiculty with such powders appears tojbe the failure of-the vat dye, upon being added to water or a printing paste, to revert to its'original degree of fineness and uniformity of dispersion, which failure is apparently brought "about, in part'at least,

by changes inthe physical condition of the vat dye'during the drying. a

While the foregoing objections to the vat dye powders heretofore known to the art are of consequence in connection with their use in dyeing with a reduced bath or vat, owing tothe greater, period of time required for complete solution of -the vat dye in the course of preparation of the bath and its resulting increased cost of dyeing, they do not prevent the use of such powders in certain connections such as dyeing by the. reduced bath or vat process. In connection with the dyeing of textile material, by the pigment padding and. printing processes, however, the said objections areordinarily of so great importance as to render such powders of little value for use in the latterprocesses. Thisis due to the fact that, in

\ both the pigment padding and printing processes,

the insoluble vat dye is ordinarily converted to the soluble-form in contact with the fiber to be dyed, and consequently uniformity of dispersion of the dye in-the padding liquor or printing paste is required to avoid unevenness of'shade and/or streaking, extremely fine subdivision 'of the in- The present invention is based upon the discovery that the readily soluble salts of the hereindescribed acid alkyl esters of polybasic inorganic acids possess a combination of properties which render them of particular value for the production and manufacture of vat dye preparations in the form of suspensions, pastes and powders, and especially for the manufacture of vat dye powders which can be used as initial material for the preparation of dye baths and pastes for dyeing textile fibers, in particular by printing and pad and jig processes. Thus, the soluble salts of the said reaction products of sulfuric acid or chlorsulfonic acid upon the aliphatic monohydric alcohols which contain 5 or less carbon atoms, which products are considered to be acid alkyl sulfates corresponding with the formula ROSOaH (in which R. is a hydrocarbon radical containing not morethan 5 carbon atoms), as well as others of the hereindescribed soluble salts of acid alkyl esters of inorganic polybasic acids, have the faculty of rapidly entering into solution in water and other aqueous suspension media for vat dyes. They furthermore have little or no tendency to foam and lather,'which is in contradistinction to the foaming and lathering action of the sulfuric acid esters of alcohols of high molecular weight (e. g.,'lauryl'sulfate). In addition they act as dyeing assistants, e. g;, in the absorption or adsorption of the. reduced compounds of the vat dyes by the fiber, and in the penetration of woven fabric by'the reduced compounds of the vat dyes during the 'developing'steaming or ageing operations.

The invention accordingly comprises the compositions havingthe-properties, ingredients and proportions of ingredients, exemplified in the compositions hereinafter disclosed, and the processes comprising steps and their relation exemplified in the processes hereinafter disclosed. The scope of the invention will be indicated in the appended patent claims.

In the preparation of a vat dye composition of the present invention, a vat dye is mixed with one or more of the soluble salts of the acid alkyl esters of polybasic inorganic acids more fully identified hereinafter. The said preparation of the compositions of the present invention may be carried out in a number of ways, for example, by intimately grinding the salt of the acid alkyl ester in the solid form with a solid form of the vat dye. The compositions of the present invention are preferably prepared by dissolving the said salt of the acid alkyl ester in an aqueous dispersion or suspension of the vat dye, which preferably contains a dispersing agent, with or with- 'out addition of fillers and/or other substances desired in'the final product, and drying the resulting mixture, preferably with agitation and preferably by evaporation to substantial dryness. I have found, by removing water, as by evaporation to substantial dryness, from an aqueous. disperson or suspension of a vatdye containing one or more of the soluble salts of thesaid acid alkyl esters, that the final product has the appearance of a solid dispersed suspension. In those cases where a very large amount of the salt of the acid alkyl ester is employed, a part of said salt may crystallize during the evaporation, but the crystals are so finely divided and evenly distributed throughout the whole composition, that the product appears to be substantially homogeneous.

action products resulting from the interaction of an aliphatic monohydric alcohol containing or less carbon atoms with a polybasic inorganic acid or suitable derivative thereof and which are considered to be partial esters of polybasic inorganic acids consisting, on the one hand, of a radical of an inorganic polybasic acid in which at least one of the replaceable hydrogen atoms ispresent and,

the expression lower alkyl hydrocarbon radical denotes an aliphatic hydrocarbon radical containing .a maximum of 5 carbon atoms. The

. salts of the said acidalkylesterswhich contain a radical of sulfuric, boric, phosphoric or thiophosphoric acid, and especially of sulfuric or phosphoric acid, are of particular interest in connection with the present invention. These par- 1 tial esters (which are herein designated as acid alkyl esters) may be represented by the formula (Emir-Atom).

in which R represents an aliphatic hydrocarbon radical which contains less than 6 carbon atoms,

A represents the residue of the inorganic acid (as for example the radical $02, the radical PO,

theradical B, ,etc.),

n represents the number of hydrogen atoms, in

the uncombined polybasic acid from which the ester is derivable, which are replaceable by a metal (hereindesignated asrepl aceable hydrogen atoms), and :c is one or more but not greater than n-1.

the parent polybasic inorganic acid has not been replaced.

It is to be noted in the case of acid alkyl esters which are derivatives of polybasic acids containing 3 or more replaceable hydrogen atoms in. which more than one of said hydrogen atoms have been replaced by organic radicals, the said organic radicals (represented by R in the above formula) may be the same or different. i The alkyl ester salts employed in accordance with the present invention comprise the solublesalts of the herein-described acid alkyl esters; e. g., those resulting from the combination of the said acid alkyl esters with any suitable metal or base, including the organic bases, producing salts having good solubility and also preferably a finely crystalline or amorphous form in the solid For example, alkali metal, alkali earth state. metal, ammonium, etc. salts may be employed or the salts formed by the interaction of the-said acid alkyl esters with such organic bases as alkyl amines (particularly the hydroxy alkayl amines), pyridine, guanidine, urea or other salt-forming organic ammonium bases.

The said alkyl ester salts employed in accordance with the present'invention may be prepared in any manner well known to the art; as for example by the treatment of the corresponding alcohol, in the presence or absence of a solvent or diluent, with a suitable inorganic reagent (such' as phosphorus chloride or oxychloride, concentrated sulfuric acid and/or chlorsulfonic acid,

etc), and neutralization of the resulting acid alkyl ester withan inorganic or organic base i which forms a readily soluble salt with said acid acid or chlorsulfonic acid may contain varying amounts of sulfonic acids which are sometimes produced due to secondary reactions; the presencegef such sulfonic acids, however, does not impair the usefulness of the monoalkyl sulfuric acids in accordance with the present invention.

and. boric acids; diamyl dithiophosphoric acids;

etc.

Of special interest in connection with the present invention are the alkali metal salts of the sulfuric acid mono esters of the various alcohols which contain not more than 5 carbon atoms, in-

cludingthosewhich contain single or multiple bonds, straight chains and branched chains. Thus, there may be particularly mentioned, by way of illustration, the sodium or potassium salts ofthe following: ethyl sulfuric acid; normal and isopropyl sulfuric acids; the monosulfuric acid ester of methyl ethyl carbinol; normal, iso-, and tertiary-butyl sulfuric acids; the mono sulfuric acid esters of pentasol, of'secondary butyl carbinol, and of methyl-n-propyl carbinol; pentene-2- sulfuric acid; normal amyl sulfuric acid; tertiary amyl sulfuric acid; amylene sulfuric acid; etc. The salts of the monoalkyl sulfuric acids which contain from 3 to 5 carbon atoms in the alkyl group are of especial value in the production of vat dye composition in accordance with the present in vention. Those in which the alkyl group comprises an iso-alkyl radical (as for example, an isopropyl radical:

I CH:

CH- CH: an isobutyl radical:

CH- cmonz etc.) are somewhat superior in their action tothose in which the alkyl group is a normal or straightchain radical, although they are somewhat more hygroscopic than those in which the alkyl group is anormal or straight-chain radical.

The said sulfuric acid mono alkyl esters may be prepared in any manner well known to the of 'chlorsulfonic acidto form the sulfuric acid mono ester of the alcohol, the mixture then may be blown with air to remove hydrogen chloride formed, and subsequently stirred with water.

Mixtures of said salts of acid alkyl esters may also be employed in accordance with the present invention; as for example the salts of alkali metals or organic bases with the commercially available and cheap mixtures of alkyl sulfuric acids resulting from the sulfuric acid treatment of gaseous and lighter liquid unsaturated hydro carbons, such as mixtures produced in the recovery and removal of unsaturated hydrocarbons in the production and purification of gasoline in the so-called cracking process'of petroleum,

distillation.

Inasmuch as the quality and dispersibility of the resulting dye composition is dependent to a considerable extent upon the original degree of dispersion of the dyein the dispersion or suspension before drying, the vat dye is preferably 'ent, anti-foaming, assisting, wetting, catalytic,

enoly'zing, or other suitable action in the subse-v quent use of the compostions may also be incorporated into the compositions of thepresent intreated in the highly dispersed form. A suitable dispersing agent is preferably included in the dis-v persion or suspension so as to aid in preventing precipitation and-agglutination of the dye particles during the drying and to increase the fluidity and render easier the'incorporation of the monoalkyl sulfuric acid salt. Among the dispersing agents which may be employed for this purpose there may be mentioned for example, the sulfonic acids of benzene, hydroxybenzen'es, naphthalene,

hydroxynaphthalenes, their nuclear alkyl, nu.-. clear aralkyl and hydrogenated derivatives, as,

well as aldehyde condensation products thereof (as for example 2,6-naphthalenedisulfonic acid, 1.7-naphthalenedisulfonic acid, 2.8- naphthalenedisulfonic acid, isopropylnaplithalenesulfonic acids, dibutylnaphthalenesulfonic acids, amylna phthalcncsulfonic acids, butylbenzylnaphthalenesulfonic acids, cyclohexylnaphthalenesulfonic acids, methylene-di (betanapth'alenesu1- ionic acid), acetaledi (beta naphthalenesulfonic acid), benzal-di beta-naphthalenesulfonic acid),

methylene di (diisopropylnaphthalenesulfonic acid), etc.); sulfite cellulose waste liquors and,- their mildly oxidized. products and evaporated residues; sulfonated resins; abietene; abietine and abietane sulfonic'acids; and the like, as well as mixtures'of two or more of such substances.

Ifdesired, additional substances having dilu vention,,preferably while the latter are in the form of aqueous suspensions.

In order that the compositions may be in a A more satisfactory form for subsequent use, the

mixture of vvat dye inaqueous dispersion and salt.

scales or grains which may be used as such; or;

the paste, with or without preliminary. evaporation may be admixed with a, suitable hydrateforming soluble salt-in an anhydrous condition and the admixture stirred to produce a dryproduct. If desired, the dry products may be disintegrated into a powder in any suitable manner,

as for example by grinding in a ball mill, and;

subsequently screened.

' The amount-of salt of acid alkyl ester employed inthe'preparation of the compositions of the'present invention maybe varied over-a considerable range, depending in part upon the nature and concentration of the vat dye in the composition, the use to which the composition is to be put, and whether or notother diluents andother materials having a catalytic, assisting,

wetting, enolyzing, dispersing, or other action are included in the composition. For example,

an ideal vat dye composition in dry form is obtained by replacing all of the water in a vat dye paste with an equal amount of said alkyl estersalt, in which casethe' composition of the powder may be for example:

' Per cent Vat dyelactualjdye solids) 10-20 Dispersing agent (e. g. Leukanol) 1- 2 Salt of the acid alkyl ester; 89-78 While a powder composition having such a large content of the alkyl ester salt is an extremely advantageous product, in that it is applicable for the preparation of vat dyes of all classes in the powdered form which, when slurried with water, yield pastes which in many the preparation of a paste useful as a pigment (as for example for the coloring of paper and the like), only a sufficient amount of alkyl ester are quite suitable, such as sucrose (ordinary cane or beet sugar), .cerelose (or corn sugar), etc. Dextrines, glue, gelatin, gum arabic, or

other substances included in the general class of so-called protective colloids also may be used; as well as other products which do not cause precipitation of suspended vat dye particles or otherwise produce specky printing pastes (as for example, urea, variousother highly soluble amides, etc). i I

When the vat dye powder compositions of the present invention are to be employed in the preparation of vat dye printing pastes and it is desired to take advantage of the solubilizing action of the said alkyl ester salts, andespecially the monoalkyl sulfuric acid salts, in the preparation of the printing pastes and-their assisting action in the printing operation, a larger amount of said salts will ordinarily be employed than would be necessary merely for the preparation of a readily dispersible vat dye powder. As has been pointed out hereinbefore, the specific amount of of printing pastes with the aid of vat dye powders of the present invention, that the printing pastes frequently show signs of prereduction, even in the absence of printing catalysts or reduction accelerators employed in the art, such as aoaasae celerators," hydrotropic and/or enoiyzing substances, in addition to .or in replacement of part of other diluents.

It is to be noted that under the term hydrotropic substances are to be understood not only the substances specially enumerated by Neuberg and "Iamba chemische Zeitchrift, vol. 76, 1916, page 107 if., V 15 and Tamba, Biochemische Zeitchrift, vol. 145,

(compare Carl Neuberg, H

1924, page 415; Carl Neuberg, Sitzungsberichte der Koengl. Preussischen Akademie der Wissenschaf ten, 1916, page 1034), but all of those substances, which comply with the definition of the word hydrotropic as given by Neuberg. -As

, salt of ethyl sulphonic acid, potassium or soexamples of such substances the following may be mentioned: urea, substituted ureas, thiourea, hexamethylene tetramine, the potassium dium isovaleratathe alkali metal salts of the following acids: isobutyric acid, phenylacetic acid, benzoic acid, o-toluene-carboxylic acid,

salicylic acid, the benzene sulphonic acids, p-

toluene-sulphonic acid, the benzene sulphinic acids, 1.4-toluene sulphinic acid, naphthalene sulphonic acids, aniline sulphonic acids and substitution products thereof, naphthylamine sulfonic acids (as for example, l-amino-naphthae ,lene-3.6.8-trisulf0nic acid) picolinic acid, hydro aromatic carboxylic or suiphonic acids, and the a which It will be further noted that substances like. are not, strictly speaking, hydrotropic substances ,but which possess enolyzing propertiesarefincluded, as for example l-naphthalene sulphonic acid (sodium salt). I r

' present invention is of The presence of enolyzing substances in vat dye powders prepared ,in accordance withthe particular advantage in 5 connection with vat dyes of the indigoid and thioindigoid series, inasmuch as they tend to minimize or prevent isomerization of V the reduced vat dye to theketo form. v It may be noted, in connection with the use oflthe vat dye pastes andpowders of thepresent invention in dyeing and printing, that thevat dye pastes and powders of the present invention may be substituted in ordinary dye baths,

padding liquors and printinepastes in place of, the usual vat dye pastesfion the basis of the weight of the dye in the pasteor powder) without otherwise changing the proportions and ingredients of said compositions.

The vat dye compositions of the present in- H vention are particularly valuable for dyeing and (unbleached celfabrics and the like) inasmuch as the dyeings and prints ob tained" with the aid of such compositions have exprinting so-called gray goods" ceedingly :high tinctorial value and excellent penetration,

particularly when. compared with dyeings and prints made in the absence of the acid alkyl esters, and their salts, employed in accordance with the presentinvention.

The invention may be employed in connection with vat dyes of all types including those derived from anthraquinone, 'indophenois, various indigoid. thioindigoid and indirubin compounds, etc.; as ior example, indanthrones, pyranthrones, fia'vanthrones, dibenzanthrones, isodibenzanwt-lirones, perylene quinones, anthanthrones, di-

benzpyrene,

quinones, anth'rimido-carbazols,

naphthacridones, indigo, thioindigo, indirubin,

etc., including derivatives thereof, such as their halogen, nitro, sulfur and/or alkoxy derivatives.

The invention will be further described in coninection with the following specific examples (in which the parts are by weight), which are given to illustrate the invention. It will be realized,

however, that the invention is not limited thereto but thatchanges may be made in the materials treated and their proportions, manipulative steps,

1 and other conditions without departing from the scope of the appended patentclaims.

Example 1 .400. parts of indigo paste (containing 20 per cent. of pure indigo as shown by indigotine titration and resulting from the pre-.

a per cent'of indigo which, when added to water,

dispersesreadilyr When employed for the preparation of an indigo vat with the aid of the usual reducingagents (for example, alkaline sodium hydrosulfite), the powder reduces very rapidly andproduces a clear vat which dyes cotton even, blue shades of high tinctorial value. Instead of the normal butyi sodium sulfate, an equal amount of normal amyl sodium sulfate, (C5H1'1OSOsNa) or of any of the other salts of acid alkyl esters hereinbefore mentioned, and especially lower monoalkyl sulfuric acid soluble salts may be used.

Example 2.To 100 parts of the chlorinated indanthrcne vat dye known as National Carbanthrene Blue 308 (Color Index No. 1114) in the formof an aqueous suspension or commercial paste'vcontaining 18 per cent of total dye solids,

, there are'added with stirring 2 parts of Leukanol (or 6 parts of a 30 per cent solution of Leukanol) 50 parts of cane sugar, and25 parts of dextrine. The suspension is stirred until homogeneous, and then 5 parts of secondary butyl sodium sulfate are added and the mixture is stirred until solution of the alkyl sulfate is complete. The resulting mass, either as such or after evaporation, may be used as a paste; or it maybe evaporated to dryness, ground and screened, as in Example 1, to

produce a powder that is readily dispersed when added to water. The product, either in the form of paste or powder, gives uniform dyeings of high tinctorial value when employed to dye fabrics in accordance with standard practice, and especially by the pad andjig method. Instead of sec rial "is dissolved, and is then evaporated to'dryness, ground to a powder, and screened through a 60 mesh screen. The resulting product is a'violet colored powder Whichisfreadily dispersed upon; 1 adding to water and is especially suitable for dyeing. fibers by the pad andjjigfprocess. When the powderlis' made intoqa printing paste containing the usual additional ingredients, and the resulting I paste is. employed to print a textilefabric which 10,

is then dried, aged, developed and soaped in accordance with 'the standard procedure, abright violet, mum 'penetrated,f and,levelprint is'prov duced. Instead of the ln orm al-butyl sodium sulfate, the potassium salt of the acid sulfuric ester of dimethyl ethyl carbi'nolor readilysoluble salts, ,of any of the otheracid esters above disclosed may be" used;

Example '4.-' 10(i"'p artsof National Carbam threne Violet 2R Paste (cf. Example 3) are mixed with 25 parts of cane sugar and 68 parts of iso- ,propyl sodium sulfate v on," V I germane) C a,

and the mixture is stirrediiuntiljthe latter are dissolved. The resulting suspension is. thenfevapo rated to dryness, groundand'screenedy 100 parts of a violet powder is obtain whichpis' suitable for dyeing by all-known methods. It is especially;useful formaking'pastes tofbe used in dyeing by the-printing process.

Example 5. l parts" i the dye known as NationalVat Orange R (Color Index 1217) invtheform'of an aqueous paste containingaboutll" per cent of dye solids, are mixed withZ parts of Leukanol and 87 parts ofethyl' sodium, sulfate (C2Hs0SOaNa) until solution'of the latter is complete. The resulting suspension is evaporated to dryness, ground and screened. instead ofthe ethyl sodium sulfate other salts of thelower alkylsulfates may b'e employed. -100 parts of a Vat Orange R powder are thus obtained, which, when employed in the preparation of a printing paste (for-example by mixing150 partsof the powder-with 200parts of British .gui'n, 140 partsof potassium carbonate, 80 parts of sodium formaldehyde sulfoxylate, 50 parts of glycerin, and 380parts of water). and utilized in the printing .of. cotton in accordance withthe usual procedure, produces prints which in heavy shades'are about 20m 25 per cent greater in strength than corresponding prints made without the alkylsodium sulfate. I i-addition, the presence of the monoalkyl sulfuric acid salt results 'in'a' much greater brilliancy of.-shade andmore complete penetration of the, material, so that in many instances there are no back sides-and the fastness to crocking is-much enhanced.

-- alkyl esters whichcontain-an iso-radic'al (as for It may be; noted that the soluble salts of acid example, the isopropyl radical, the isobutyl radical, etc.) are preferably employed in connection with'yat dyes of the f thioindigoid series when the latter are to .be employed for the preparation of printing. pastes, in view of" their superior action inthe printing process. i

-E zcdmple 6.-'[-'I 'o 100 partsfl of .National Vat Orange RPaste (employed in Example 5), there are added 2 parts of Leukanol,;4 parts Tof the potassium salt of 2-carboxy benzophenone-le sulfonic a'cid 50 parts isobutyl-sodium sulfate,

and 33 parts of dextrine. The resulting mixture isstirred until all soluble matter'is dissolved, and the resultingsuspension is evaporated to dryness,

thioindigoid vat.

ground and screened. A bright orange pigment is obtained which disperses readily in vat printing pastes. When printed on textile fabrics of all kinds, it yieldsa very brilliant orange of increased strength over prints made fro'mtheioriginalVat'Oran'ge R Paste in the ordinary method. The potatssium Z-carboxy-bnzophenone- Gil 4"-sulfonate acts as an assistant or adjuvant,

as more fully disclosed and claimed in, my application Serial'No. 723.332, filed May 1,.1934.

, Example 7.-To 100 parts of the vat" dye known as National Vat Pink FF (6.6'-dichl0r'-4;.4-dimethyl thioindigo) in the form of an aqueous j paste or suspension containing 15 per cent of dye solids, there are added 2 parts of Leukanol, 64

parts of isobutyl sodium sulfate and i8 parts of cane sugar. The. mixture is stirred until the-soluble material is all dissolved, and is" then evaporated to dryness, ground and screened. 'A highly colored pink pigment is obtained which is readily dispersed in water or in sodium sulfate are added The mixture is stirred until all the soluble matter is completely dissolved, and is then evaporated to dryness,,ground and screened. 100 parts of a. blue powder are obtained which is of especial value for the preparation of printing pastes. The cane sugar employedin this example may be replaced by dextrine, gum'arabic, glue or other so-called protective colloids, alone'or with the addition of any of the substances above referred to as hydrotropic'or enolyzingsubstances.

Example 9.To 100 parts of National Carbanthrene Blue GCD Double. Paste (Color Index .1113) containing 16.5 per cent of dye solids and 1 per cent of Leukanol, there are added 50 parts of isobutyl sodium sulfate and 32.5 parts of urea, and the mixture isstirred until the latter are dissolved. The resulting suspension is evaporated to dryness, ground and screened. A very readily dispersible vat powder is obtained which is suitable for printing as well as dyeing.

' Example 10.-To 100 parts of'National Carbanthrene Fl-avine GC (cf. U. S. P. 993,992) in v the form of a commercial paste containing about 23 per cent of dye solids and about 2 per cent of Leukanol, there'are added 24 parts of sucrose,

55 parts of the sodium salt of the monosulfuric acid ester of secondary butyl carbinol CnHs v /CHCHIOSO8NB CH;

and 1 part of the disodium salt of 2.6-dihydroxyanthraquinone. .The mixture is stirred until all soluble matter is dissolved and the resulting suspension is evaporated to dryness, ground and screened. 100 parts ofa brilliant yellow powder is obtained which is suitable for dyeing and printing.

In the preparation of the compositions of the present invention, it is not necessary to employ a previously prepared dyestufi paste but the filter cakes and other separated forms of the dye may be employed; as for example, the press cakes resulting from the filtration of aqueous suspenas illustrated by the following example;

Example 11.-2 parts of the sodium salt of anthraquinone-Z-sulfonio acid are dissolved in 2031 parts of water, with the aid of heat if necessary, 100 parts of dextrine are added, and

the mixture is stirred until a smooth paste is obtained; 110 parts of National Vat Orange R (in the form of a press cake containing 21 per cent of dye solids) and 15 parts of Leukanol solution (30 per cent) are then added. The mixture is stirred until a well-dispersed thin fluid suspension is obtained. Then '74 parts of isobutyl sodium sulfate are added, and stirring is continued'until the latter is dissolved. The resulting mass is evaporated with'stirring until a thick paste "is obtained and is then dried, ground and screened as in the foregoing examples. 200

National Carbanthrene R d Violet RNX 1 i National Carbanthrene Brilliant parts of a brilliant orange powder is thus obtained having similar properties to those of the product of Example 6.

In the above examples other readily soluble salts of the hereindescribed acid alkyl esters, and especially other salts of alkyl sulfuric acids which are included within the i formula RCSOsH (in which R is a hydrocarbon radical containing a maximum of '5 carbon atoms), may be employed instead of all or a part of. the monalkyl sulfuric acid salts thereindisclosed. The vat dyes disclosed may be replaced by any other vat dye; as for example: a

National Carbanthrenelellow G--- Color IndexNo. National Carbanthrene G o l d e n 1 Orange G Color Index No. National ,Carbanthrene G old e n Orange 2R Color Indet No. National Carbanthrene Blue Green .FFB Color Index No. National Carbanthrene Violet 2R--- Color Index No. National Carbanthrene Dark Blue i olor Index No. 1099 Color Index No. 1161 Color Index No. 1101 Green supra National Vat Red Violet RH (Cf. U. S. P. 916,029) National Vat Scarlet G Color Index No. 1228 National Vat Brown G (di aphthyltliioindigoL; ational Vat Violet R Color Index No. 1222 National Brilliant Indigo B- Color Index No. 1190 National Brilliant Indigo 4B Color Index No. 1184 National Brilliant Indi 4G Color Index No. 1189 National Carbanthrene ed BN- Color Index No. 112 National Carbanthrene Brown A Color Index No. 110} National Carbanthrene Green B Color Ind ex bio. 11 2 National Carbanthrene Olive-Bani Color Incex 1N0. 1100 1 National Vat Yellow G ;Color Inoex No. 1196 National Carbanthrene Red AFF Color Inr ex No. 1133 National Carbanthrene Blue RS Color Index No. 1106 National VatPink BG Color Index No. 1210 National Vat Yellow R g Color Index No. 1170 National Carbanthrene Blue 3G-- Color Index No. 1109 Furthermore, mixtures of two or more vat dyes may be employedwhen it is desired to obtain compound shades, such as scarlets, browns, navy blues, and blacks.

- evaporated r'nixture.

fcor dance with the present invention by admixing a suitable hydrate forming soluble salt in an anhydrous condition with the paste, whereby a dry product is formed by formation of a hydrate of said salt. Thus, as will be further illustrated by the following specific examples, trisodium phosphate, sodium sulfate, sodium acetate or other suitable hydrate-forming soluble salts (having regard for the nature and intended use of the product) may beadmixed in an anhydrous condition (in the anhydrous form or a partially dehydrated'form) by stirring with a vat dye composition of the present invention in the form of a paste, preferably in the form of a partially The resulting dry mixture maybe ground and screened to form a powder. This latter procedure has the advantage of saving time and labor as compared with the evaporation procedure of drying. Furthermore, the danger of decomposition of the products by lengthy "denser (less bulky) and dusts less, and consequently is cheaped to ship on a volume basis and more convenient to use.

Example 12.-300 parts of indigo paste (containing 20 per cent of pure indigo, as shown by indigotin titration), are stirred with 2 parts of dry Leukanol until a thin fluid paste is obtained; parts of normal butyl sodium sulfate are then added, the mixture is stirred until solution of the alkyl sulfate is complete, and the resulting mixture is evaporated with stirring until a thick paste containing about 19 to 20 per cent of water is formed. 15 parts of anhydrous trisodium phosphate are then added and the mass is intimately mixed until a dry product is obtained. There is thus produced 100 parts of the dry composition containing 60 per cent of indigo. Upon grinding the product and screening through a screen of fine mesh, a fine dry powder is obtained. which disperses very readily and may be used for all dyeing purposes.

Example 13i-To 100 parts of the pyranthrone vat ,dyestuff known as National Carbanthrene Golden Orange 2 RT Paste (Color Index 1097), containinglO percent of dye solids in the form of an aqueous suspension and 1 per cent of Leukanol, there are added parts of cane sugar and 50 parts of isobutyl sodium sulfate. The mixture is evaporated with stirring until a paste containing 18 to 20 per cent of water is obtained. 15 parts of anhydrous trisodium phosphate are sodium sulfate, 1 part of the sodium salt of anthraquinone-Z-sulfonic acid, and 10 partspf cane sugar. The mixture is stirred to dissolve the sol- "uble material, and then evaporated with stirring until a paste containing approximately 16 per cent of'water is produced. "The resulting paste is intimately'mixed withl2 parts of anhydrous. trisodium phosphate whereby a dry product is obtained, which, when ground and screened, results in a bright orange powder having advantageous properties similar to, those of the prodnot of Example 6.

then added and themixture is stirred until a dry a mass is produced. Upon grinding and screen- 'wmie the invention has been described par ticularly with relation to the preparation of compositions which are especially suitable for the dyeing and printing of textile fabrics, it is to be understood that the invention is 'notlimited thereto but that the readily dispersible powders,

of the present invention are also of especial utility in the preparation of aqueous suspensions of the dyestufi forum in the pigment form for the dyeing of paper, the tinting of fibers and other material, and .the like;

It is further to be noted that the vat dye compositions of the present invention containing 'soluble salts of acid alkyl esters may also be utilizedas components of discharge and resist printing preparations as well as of the dyeing and printing compositions above described. v This application is a division of my application Serial No. 673,031, filed May 26, 1933, for Art of dyeing and coloring, and is in part a continuation of my application Serial No. 673,030, filed 1 .May 26, 1933, for Vat dye composition.

I claim:

l. A vat dye composition comprising a vat dye and a soluble salt of an alkylsulfuric acid corresponding with the formulaROSOfl-Lin which R represents a hydrocarbon radical containing less than 6 carbon atoms. 3

' 2. A vat dye composition comprising a vat dye and a soluble salt of an alkyl sulfuric acid corresponding with the formula ROSOsH, in which g R represents a hydrocarbon radical containing less than 6 carbon atoms, said composition being in the form of powder which dispersesreadily when added to water-. 7 I a 3. Avat dye composition in solid form for use in coloring, dyeing andtextile printing which comprises a vat dye, a dispersing agent, and a soluble salt of an alkyl sulfuric acidcorrespondthe NH4 radical.

5. A vat dye composition in the dry solid form comprising a vat dye'and an alkali metal salt of an alkyl sulfuric acid containing 3 to 5 carbon atoms in the alkyl group, said salt corresponding with the formula ROSOaM, in which R repre'' sents a saturated hydrpcarbonradical containing from 3 to 5 carbon atoms, and M represents an alkali metal. i

' 6. A vat dye composition in solid form adapted for use in textile printing which comprises a vat dye, an alkali metal salt of analkyl sulfuricacid containing less than 6 carbon atoms, said salt corresponding with the formula RQSOaM, in

which R represents an open-chain hydrocarbon radical containing less than 6 carbon atoms and M represents an alkali metal, and a material selected from the class of carbohydrates, printing catalysts, assistants, 'hydrotropic substances,-. and

enolyzing substances. k I 7. A 'vat dye composition in, solid form'for use in textile printingwhichv comprise's'avat dye and the sodium salt of an alkyl sulfuric acid containing less than 6 carbon atoms in the'alkyl group, said salt corresponding with the formula ROSOaNa, in which R represents an alkyl radical containing less than 6 carbon atoms, such as is obtainable by drying an aqueous mixture comprising the vat dye and the sodium salt of the alkyl sulfuric acid.

8. A vat dye composition in solid form adapted for use in textile printing which comprises a vat dye selected from the group of anthraquinone, indigoid and thioindigoid vat dyes, and the sodium salt of an alkyl sulfuric acid containing 3 to 5 carbon atoms in the alkyl group, said salt corresponding with the formula ROSOaNa, in which R represents a saturated hydrocarbon radical containing 3 to 5 carbon atoms.

9. A vat dye composition in dry solid form. which comprises an intimate mixture of a vat dye, an aldehyde condensation product of an aromatic sulfonic acid, a carbohydrate and a highly soluble salt of a monoalkyl sulfuric acid containing less than 6 carbon atoms.

10. A vat dye composition in dry solid form, which comprises an intimate mixture of a vat dye, a formaldehyde condensation product of a naphthalene sulfonic acid, a carbohydrate, and sodium isobutyl sulfate.

11. A method of making a vat dye composition which comprises incorporating a, soluble salt of an alkyl sulfuric acid corresponding with the formula ROSOsH, in which R represents a hydrocarbon radical containing less than 6 carbon atoms, into an aqueous suspension comprising a vat .dye and a dispersing agent, and drying the mass.

12. A method of making a vat dye composition which comprises incorporating a soluble salt of an alkyl sulfuric acid having the formula ROSOaM, .in which R represents an open-chain hydrocarbon radical containing less than 6 carbon atoms and M represents an alkali metal, into an aqueous suspension comprising a vatdye and an aldehyde condensation product of a naphthalene sulfonic acid as a dispersing agent, and drying the mass. 4

13. A method of making a vat dye composition,

which comprises incorporating an alkali metal salt of a monoalkyl sulfuric acid containing 2 to 5 carbon atoms into an aqueous mixture comprising a vat dye, a formaldehyde condensation product'of a naphthalene sulfonic acid, and a carbohydrate, and drying the mass.

14. A vat dye composition in the form of an aqueous paste comprising a vat dye, an aldehyde condensationv product of a naphthalene sulfonic acid as a dispersing agent, and a soluble salt of 1 an alkyl sulfuric acid containing less than 6 carbon atoms in the alkyl group, saidsalt corresponding with the formula ROSOaM, in which R represents an open-chain hydrocarbon radical containing less than 6 carbon atoms, and M represents an alkali metal.

15. A vat dye composition in the form of an aqueous paste comprising a vat dye, a formaldehyde condensation product of a naphthalene sulfonic acid and an-alkali metal salt of an alkyl sulfuric acid containing3 to 5 carbon atoms in the alkyl group, said salt corresponding with the formula ROSOsM, in which R represents a sat-. urated hydrocarbon radical, containing from 3 to 5 carbon atoms, and M represents an alkali metal.

16. A vat dye composition in the form of an aqueous paste comprising a vat dye, a dispersing agent, and a soluble salt'of an acid alkyl ester consisting on the one hand of a radical of an inorganic polybasic acid in which at least one of the replaceable hydrogen atoms is present and on the other hand 'of one or more lower alkyl hydrocarbon radicals directly linked to the inorganic radical; 17. A vatdye composition comprising a vat dye and a soluble salt of an acid alkyl ester consisting on the one hand of a radical of an inorganic polybasic acid in which at least one of the replaceable hydrogen atoms is present and on the other hand of one or more lower alkyl hydrocarbon radicals directly linked to the inorganic radical.

3 18. A vat dye composition in the dry solidform comprising a vat dye and an alkali metal salt of an acid alkyl ester consisting on the one hand of a radical of an inorganic polybasic acid in which at least one of the replaceable hydrogen atoms is present and-on the other hand of one or more lower alkyl hydrocarbon radicals directly 1g linked to the inorganic radical.

19. A vat dye composition in dry solid form.

which comprises an intimate mixture of a vat dye, an aldehyde condensation product of an arcmatic sulfonic acid and a highly soluble salt of an "acid alkyl ester consisting on the one hand of a radical of an inorganic polybasic acid in which at least one of the replaceable hydrogen atomsis present and on the other hand of one or more lower alkyl hydrocarbon radicals directly linked to the inorganic radical. g

20; Amethod of making a vat dye composition which comprises incorporating a soluble salt of an acid alkyl ester into an aqueous suspension comprising a vat dye and a dispersing agent, and drying the mass, said acid alkyl ester consisting on the one hand of a radical of an inorganic polybasic acid in which at least one of the replaceable hydrogen atoms is present and on the other hand of one or more lower 'alkyl hydrocarbon radicals :directly linked to the inorganic radical.

JEAN G. KERN. 

